Pearlescent pigment

ABSTRACT

The present invention relates to a pearl pigment obtained by coating the surface of a flaky powder with a colored metal or a colored metal oxide and further coating the surface of the above colored metal- or colored metal oxide-coated flaky powder with a colorless metal or a colorless metal oxide, wherein when the pearl pigment is applied onto the surface of black artificial leather in an average amount of 0.05 mg/cm 2  and the intensity of light reflected from the pearl pigment is measured using illuminant C at a 2° viewing angle with a spectrophotometric colorimeter which is provided with a sheet polarizer S on the light incident side and a sheet polarizer P on the light receiving side, the powder reflection light which is incident to the pearl pigment as a measurement sample at an angle of 45° to the direction normal to the surface of the sample and is received in the direction normal to the surface of the sample has absolute values a* and b* of 10 or less, and make-up cosmetics containing the pearl pigment.

This application is a Continuation of application Ser. No. 11/300,369,filed on Dec. 15, 2005, now U.S. Pat. No. 8,016,934.

FIELD OF THE INVENTION

The present invention relates to a pearl pigment, a process forproducing the same, and make-up cosmetics containing the same.

BACKGROUND OF THE INVENTION

There have been used a variety of coloring pigments in areas such ascoatings, plastics, printing inks and cosmetics. In recent years, therehave been used light-interference pearl pigments which are obtained bycoating the surface of flaky powder with titanium oxide, iron oxide orthe like to obtain a bright color and a certain kind of design onproducts.

In commonly used pearl pigments, which are obtained by coating thesurface of flaky powder with a colorless metal oxide such as titaniumoxide, the thickness of the coating is varied, to produce a variety ofinterference colors. It is known that, for brighter interference colors,materials with different refractive indexes should be multi-layered.There have been proposed various methods for multi-layering suchmaterials, and there are pearl pigments of multi-layer construction onthe market, indeed. Meanwhile, in pearl pigments of multi-layerconstruction obtained using a color metallic compound such as ironoxide, it is also possible to obtain bright interference colors. Suchpigments are, however, affected by the color of the color metalliccompound, and there have been only pearl pigments having a color ofsimilar shade to that of the color compound. For example, pearl pigmentsobtained using iron oxide each have a color of a reddish shade. In otherwords, no multi-layered pearl pigment in which the color of the colorcompound used as an inner layer is controlled and thus interferencecolors are produced without restrictions by the color of the colormetallic compound itself has been known.

For example, in JP-A-6-100794 there are proposed multi-layer pearlpigments obtained by forming an iron oxide layer on a platelet-shapedpowder and con inn the powder with the iron oxide layer with an aluminumcompound. This proposal relates to pigments having a color of a reddishshade and a process for producing the same, and therefore provides onlypearl pigments having a color of a reddish shade. In JP-A-7-11161 andJP-A-8-259840, there are proposed multi-layer pearl pigments obtained bycoating iron oxide coated platelet-shaped powder with a colorless metaloxide such as titanium oxide. These proposals are, however, differentfrom the above described proposal only in the kind of the colorlessmetal oxide used, and like the above proposal, they provide only pearlpigments having a color of a reddish shade. There is nothing describedof obtaining pigments having a hue other than red in thosespecifications.

Meanwhile, of cosmetics using coloring pigments, make-up cosmetics arerequired to change users' skin texture when they apply them to theirskin, and powders that give rise to strong diffuse reflection orspecular reflection are used to control users' skin one and texture. Forexample, titanium oxide as a powder that gives rise to strong diffusereflection or a spherical powder is blended with make-up cosmetics tocreate a matte finish, or a platelet-shaped powder, such as mica,sericite or talc, which gives rise to strong specular reflection isblended with make-up cosmetics to impart a lustrous finish. To covercolor non-uniformity such as pigmented spots or freckles, pigmentshaving good hiding power such as titanium dioxide or iron oxide are alsoblended with make-up cosmetics.

However, the use of pigments with good hiding power causes a problem ofproducing an unnatural look, whereas the use of powders with poor bidingpower to adjust the skin tone and texture causes a problem of a decreasein the covering effect on the color non-uniformity, etc., of the skin.

To overcome the above described problems, considerations have been givento using pearl pigments that have good hiding power and are capable ofcontrolling skin luster to change the hue of the skin, in recent years.For example, when a titanium-oxide coated pearl pigment is used incosmetics for imparting a lustrous finish to the skin, skin luster canbe produced in such a direction that regular reflection of light occurs,due to the specular reflection by the pigment, but not through an angleother than that of specular reflection, and at such an angle thecosmetics impart a whitish look of the powder itself. Accordingly, whena user applies the cosmetics over a wide range, for example, to theentire face, portion directly facing its observer provides a lustrouslook, but the portion not directly facing its observer provides awhitish and powdery look, resulting in a tendency toward an unnaturalfinish. JP-A-2003-212722 describes a powder for producing natural skinluster which is obtained by coating the surface of titanium mica withalumina and silica in this order. This powder, however, still leavesunresolved the problem of a whitish and powdery look produced on theportion that does not directly face its observer.

On the other hand, there are pearl pigments in which a coating isapplied onto the colored metal oxide layer, such is iron oxide layer, onthe market. In JP-A-7-11161 and 8-259840, there are proposed multi-layerpearl pigments obtained by coating an iron-oxide coated platelet-shapedpowder with a colorless metal oxide such as titanium oxide. However, thepearl, pigments obtained are all reddish ones, and it is impossible toexpress a bright charming skin tone and texture by using them.

SUMMARY OF THE INVENTION

The present invention provides a pearl pigment having a flaky powdercoated on the surface with a colored metal or a colored metal oxide,wherein the surface of the colored metal or colored metal oxide-coatedflaky powder is coated with a colorless metal or a colorless metaloxide, wherein when the pearl pigment is applied onto the surface ofblack artificial leather in an average amount of 0.05 mg/cm² and theintensity of light reflected from the pearl pigment is measured usingilluminant C at a 2° viewing angle with a spectrophotometric colorimeterwhich is provided with a sheet polarizer S on the light incident sideand a sheet polarizer P on the light receiving side, the powderreflection light (scattered light) which is incident to the pearlpigment as a measurement sample at an angle of 45° to the directionnormal to the surface of the sample and is received in the directionnormal to the surface of the sample has absolute values a* and b* of 10or less.

Further, the present invention provides a pearl pigment having a flakypowder with a colored metal or a colored metal oxide coated on thesurface so that the average surface roughness is 10 nm or less andwherein the surface of the colored metal- or colored metal oxide-coatedflaky powder is further coated with a colorless metal or a colorlessmetal oxide.

Further, the present invention provides a process for producing a pearlpigment which includes adding an aqueous solution of a colored metaloxide precursor to an aqueous dispersion of a flaky powder so that theamount of metal ion is 5×10⁻⁴ to 12×10⁻⁴ mol/min per 100 g of the flakypowder; adding an alkaline solution to the mixed solution so that the pHof the mixed solution is adjusted to 5 to 8; separating the solid fromthe mixed solution; baking the separated solid at 500 to 1000° C. toobtain a pearl pigment; suspending the obtained pearl pigment in water;adding an aqueous solution of a colorless metal or colorless metal oxideprecursor to the suspension; adding an alkaline solution to the mixedsolution so that the pH of the mixed solution is adjusted to 5 to 8;separating the solid from the mixed solution; and baking the separatedsolid at 500 to 1000° C.

Still further, the present invention provides a process for producing apearl pigment which includes: adding an aqueous solution of a coloredmetal oxide precursor to an aqueous dispersion of a flaky powder so thatthe amount of metal ion is 5×10⁻⁴ to 12×10⁻⁴ mol/min per 100 g of theflaky powder; adding an alkaline solution to the above mixed solution sothat the pH of the mixed solution is adjusted to 5 to 8; separating theobtained solid from the mixed solution; adding an aqueous solution of acolorless metal or colorless metal oxide precursor to a dispersion ofthe solid; separating the obtained solid from the mixed solution; andbaking the separated solid at 500 to 1000° C.

Still further, the present invention provides make-up cosmetics thatcontain any one of the above described pearl pigments.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates “the method for measuring the value a* and value b*of the present invention”.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to: a novel multi-layer pearl pigmentwhich retards the production of scatter colors, takes advantage of thecharacter of a colored metal compound and produces a variety ofinterference colors free from the color tone of the colored metalcompound; a process for producing such a pearl pigment; and make-upcosmetics which contain the pearl pigment, thereby being capable ofchanging the hue of the skin while imparting a sheer dewy finish to theskin, creating a light smooth finish and producing a natural luster onthe skin.

In the present invention, value a* and value b* each indicatechromaticity standardized by Commission International de L'Eclairage(CIE) (1976). The method for measuring the values a* and b* of eachpearl pigment herein shown (see FIG. 1) is referred to as “the methodfor measuring the values a* and b* of the present invention”.

The present inventors have found that a pearl pigment obtained bycoating the surface of a flaky powder with a colored metal or a coloredmetal oxide and further coating the surface of the colored metal- orcolored metal oxide-coated flaky powder with a colorless metal or acolorless metal oxide, wherein the absolute values of the values a* andb* of the scattered light measured under specified conditions are 10 orless, produces brilliant colors and that the use of such a pearl pigmentmakes it possible to obtain make-up cosmetics capable of changing thehue of the skin while imparting a sheer dewy finish to the skin,creating a light smooth finish and producing a natural luster on theskin, and they have finally accomplished the present invention.

The pearl pigment of the present invention produces brilliant colorswhile retarding the production of scatter colors. The make-up cosmeticsof the present invention that contain the above described pearl pigmentare capable of changing the hue of the skin while imparting a sheer dewyfinish to the skin, creating a light smooth finish and producing anatural, luster on the skin. Their feeling in use, such as spreadabilitywhen applied to the skin, is also good.

The flaky powder used in the pearl pigment of the present invention ispreferably 2 to 200 μm in average particle size and 0.01 to 5 μm inaverage thickness and, from the viewpoint of suitability for blending,more preferably 2 to 20 μm in average particle size and 0.05 to 1 μm inaverage thickness. The term “average particle size” used herein meansvolume average particle size (D4) (average particle size calculatedbased on volume fraction). The measurement can be made with ease andgood reproducibility using a laser diffraction particle sizedistribution analyzer. For the thickness of the flaky particle, thedifference from the reference surface is measured with an atomic forcemicroscope and the arithmetic mean of the measurements is used as anaverage thickness.

Examples of flaky powders used in the pearl pigment of the presentinvention include: mica, sericite, talc, kaolin, smectite clay mineral,synthetic mica, synthetic sericite, platelet-shaped titanium dioxide,platelet-shaped silica, platelet-shaped aluminum oxide, boron nitride,barium sulfate, and platelet-shaped titania-silica composite oxide. Ofthese flaky powders, mica is preferable in terms of surface smoothness.

Examples of colored metals used for coating a flaky powder in thepresent invention include gold and copper. Of these metals, gold ispreferable. Examples of colored metal oxides include: iron oxide, lowertitanium oxide, copper oxide, cobalt oxide, chromium oxide and nickeloxide. Of these colored metal oxides, iron oxide is preferable.

Examples of colorless metals used for further coating the surface of thecolored metal or colored metal oxide having already been applied a flakypowder in the present invention include: titanium, zirconium, zinc, tin,silicon and aluminum. Of these colorless metals, titanium is preferable.Examples of colorless metal oxides include: titanium oxide, zinc oxideand aluminum oxide. Of these colorless metal oxides, titanium oxide ispreferable.

The pearl pigment of the present invention is such that the values a*and b* of the light reflected from the pigment powder (scattered light),which are measured in accordance with “the method for measuring thevalues a* and b* of the present invention”, are 10 or less andpreferably 5 or less.

As a measurement instrument applicable to such colorimetry, colormeasurement system GCMS series manufactured by Murakami Color ResearchLaboratory Co., Ltd. can be used.

The pearl pigment of the present invention is obtained by coating thesurface of a flaky powder with a colored metal or colored metal oxide,as described above, and the average surface roughness of the coloredmetal or colored metal oxide is 10 nm or less and preferably 5 nm orless. Since colored metals or colored metal oxides have properties ofabsorbing light having particular wavelengths, the larger the roughnessof the coating surface becomes, the more intense the scatter colorbecomes, resulting in the production of color of a low pearly luster.Decreasing the roughness of the coating surface retards the scatteringof light, which makes it possible to obtain a pigment producing lessscattered light, and hence more brilliant colors.

In the present invention, the term “average surface roughness (Ra)”indicates arithmetic average roughness, which is an average value of themeasurements obtained by measuring the range of 2 μm×2 μm using anatomic force microscope (Nanoscope III by Digital Instrument) with ascan rate set to 1.0 Hz. When the measurement is made, the dispersion ofthe pearl pigment in a solvent such as ethanol is deposited on a flatbase and then the solvent is removed to allow the pigment to closelyattach to the base. The measurement is then made with an atomic forcemicroscope.

In the pearl pigment of the present invention, the optical thickness ofthe colored metal or colored metal oxide coating layer is preferably 15to 650 nm, more preferably 25 to 650 nm, and even more preferably 250 nmor less, and even more preferably 210 nm or less. If the opticalthickness is larger than 650 nm, the absolute thickness of theabsorption layer is increased and the effect of light absorption is alsoincreased. Therefore, the pearl pigment preferably takes advantage ofthe color characteristic of the colored metal or colored metal oxideused. For example, in the case of iron oxide, when its optical thicknessis larger than 250 nm, the pearl pigment is preferably a red pigment.

The optical thickness of the colored metal or colored metal oxidecoating layer herein used means the thickness obtained by multiplyingthe geometric thickness of the coating layer by the refractive index ofthe same. In the case of iron oxide, the geometric thickness of thecoating layer is preferably 80 nm or less and more preferably 50 nm orless, in the cases were scattered light is fully retarded, if iron oxideis used as the colored metal oxide, when the optical thickness of thecoating layer is 120 to 210 nm, the interference light is gold, whereaswhen the optical thickness of the coating layer is 60 to 120 nm, theinterference light is silver. The geometric thickness of the coatinglayer is determined with a SEM.

In the present invention, the pearl pigment is multi-layered by furthercoating the surface of the colored metal or colored metal oxide with acolorless metal or colorless metal oxide, and thus, pigments of variouscolor tones, gold to green, which are not restricted by the colorcharacteristic of iron oxide can be obtained. The optical thickness ofthe colorless metal or colorless metal oxide coating layer is preferablyon average 180 to 900 nm. In case of titanium oxide, the geometricthickness of the coating layer is preferably 30 to 360 nm. If thescatter color is intense as in the case of conventional pearl pigments,the interference light is killed by the scatter color and is invisibleto the naked eye. In the pearl pigment of the present invention, sincethe scatter color is retarded, interference light having colors otherthan those characteristic of the coated colored metal or colored metaloxide, such as gold or green, can also be produced. The pearl pigmentthus obtained can produce interference colors of a high chroma, comparedwith the pearl pigment coated with a single layer.

Large optical thickness of iron oxide, etc., is advantageous whenproducing pigments having colors of a reddish shade, which arecharacteristic of iron oxide. If scatter color is retarded, brilliantred, compared with the colors of a reddish shade which is a colorproduced by conventional pigments, can be produced.

When the relationship n_(s)<n>n₀ holds, where n_(s), n and n₀ are therefractive index of a flaky powder, that of a colored metal compound andthat of a colorless metal compound, respectively, the index ofreflection can be increased, and the chroma can be enhanced.Specifically, the combination of mica (refractive index 1.58), ironoxide (Fe₂O₃) (refractive index 3.01) and titanium oxide (refractiveindex 2.5 to 2.7) is preferable.

The pearl pigment of the present invention can be produced by selectingthe rate of adding an aqueous solution of a colored metal oxideprecursor, for example, using the neutralization titration method. Theneutralization titration method is preferably used for decreasing thesurface roughness of the colored metal or colored metal oxide.

(Production Process 1)

Specifically, the pearl pigment of the present invention can be producedby: adding an aqueous solution of a precursor of a colored metal oxideto an aqueous dispersion of a flaky powder so that the amount of metalion is 5×10⁻⁴ to 12×10⁻⁴ mol/min per 100 g of the flaky powder; addingan alkaline solution to the mixed solution so that the pH of the mixedsolution is 5 to 8; separating solid from the mixed solution; baking thesolid at 500 to 1000° C. to obtain a pearl pigment; suspending theobtained pearl pigment in water; adding an aqueous solution of aprecursor of a colorless metal or colorless metal oxide; adding analkaline aqueous solution to the mixed solution so that the pH of themixed solution is adjusted to 5 to 8; separating solid from the mixedsolution; and baking the separated solid at 500 to 1000° C.

First, a flaky powder is dispersed in water and fully stirred to preparean aqueous dispersion of the flaky powder. The slurry concentration ofthe dispersion is preferably 1 to 50% by weight for coating the surfaceof the flaky powder uniformly with a metallic compound.

Examples of precursors of a colored metal oxide include ferric nitrate,ferric chloride and ferric sulfate. The concentration of the aqueoussolution of such a precursor is preferably 20 to 70% by weight.

The dispersion of the flaky powder is heated to 50 to 100° C. andpreferably to 70 to 80° C., an acid is added to the dispersion to givean acidic dispersion, and an aqueous solution of a precursor of acolored metal oxide is added to the reaction mixed solution whilekeeping the pH of the reaction solution at 2 to 4 and preferably 2.5 to3.5 by adding an alkaline aqueous solution. To realize a smooth coatedstate in which surface roughness is minimal, the aqueous solution of aprecursor of a colored metal oxide is added at a rate that allows theamount of metal ion to be 5×10⁻⁴ to 1.2×10⁻⁴ mol/min per 100 g of theflaky powder an preferably 8×10⁻⁴ to 11×10⁻⁴ mol/min per 100 g of theflaky powder. If the rate of adding the aqueous solution of a precursorof a colored metal oxide is in such a range, the scattered light isretarded, and the resultant pigment can be a preferable one.

Examples of alkaline aqueous solutions used for pH adjustment include:aqueous solutions of sodium hydroxide, potassium hydroxide, sodiumcarbonate, potassium carbonate, sodium hydrocarbonate and potassiumhydrocarbonate.

After completing the addition, the mixed solution is aged. Then, analkaline aqueous solution is added to adjust the pH of the mixedsolution to 5 to 8, and the solution is further aged. After separatingthe solid, the solid is rinsed to remove the salt and dried. The driedsol id is then baked at 500 to 1000° C. and preferably at 700 to 800° C.for 30 to 180 minutes.

Then, an aqueous dispersion of the obtained colored metal oxide-coatedflaky powder is prepared. The concentration of the slurry in thedispersion is preferably 1 to 50% by weight, from the viewpoint ofuniformly coating the surface of the colored metal oxide-coated flakypowder with a colorless metal or colorless metal oxide.

Examples of precursors of a colorless metal oxide include: titaniumsulfate and titanium tetrachloride. The concentration of their aqueoussolutions is preferably 20 to 60% by weight.

The dispersion of the colored metal oxide-coated flaky powder is heatedto 50 to 100° C. and preferably to 70 to 80° C., an acid is added to thedispersion to give an acidic dispersion, and an aqueous solution of aprecursor of a colorless metal oxide is added to the reaction mixedsolution while keeping the pH of the reaction solution at 1 to 5 andpreferably 1 to 3 by adding an alkaline aqueous solution.

Examples of alkaline aqueous solutions used for pH adjustment are thesame as described above.

After completing the addition, the mixed solution is aged. Then, analkaline aqueous solution is added to adjust the pH of the mixedsolution to 5 to 8, and the solution is further aged. After separatingthe solid, the solid is rinsed to remove the salt and dried. The driedsolid is then baked at 500 to 1000° C. and preferably at 700 to 800° C.for 30 to 180 minutes. Thus, the pearl pigment of the present inventioncan be obtained.

(Production Process 2)

The pearl pigment of the present invention can also be produced byomitting the step of baking after coating a flaky powder with aprecursor of a colored metal oxide and shifting to the step of coatingthe colored metal oxide-coated flaky powder with a colorless metal orcolorless metal oxide. Specifically, the pearl pigment of the presentinvention can be obtained by: adding an aqueous solution of a precursorof a colored metal oxide to an aqueous dispersion of a flaky powder,just like the above described production process 1; adding an alkalineaqueous solution to adjust the pH of the mixed solution to 5 to 8;separating the solid from the mixed solution; rinsing the solid withwater to remove the salt; and coating the surface of the solid thusobtained with a colorless metal or colorless metal oxide and baking thecolorless-metal or colorless-metallic-oxide coated solid in the samemanner as the production process 1.

The pearl pigment of the present invention can be used as a coloringmaterial for, for example, cosmetics, coatings, printing inks, plastics,ceramics, or glaze for glasses.

The make-up cosmetics of the present invention contain the pigmentdescribed above. The surface of the pearl pigment can undergohydrophobic treatment before use, from the viewpoint of improving thetenacity of the cosmetics. Hydrophobic treatment can be carried out by aconventional process using a hydrophobic treatment agent.

Examples of hydrophobic treatment agents which may be used include:silicone oil, fatty acid metal salt, alkyl phosphoric acid, alkali metalsalts or amine salts of alkyl phosphoric acid, N-mono long chain (with 8to 22 carbon atoms) aliphatic acyl-basic amino acid, and fluorinecompound having perfluoroalkyl group.

Examples of silicone oils which may be used include: various types ofchain silicone, cyclic silicone and modified silicone. Examples of metalsalts of fatty acids used include: salts of fatty acids having 12 to 18carbon atoms and calcium, magnesium, zinc, aluminum, or the like.Examples of alkyl phosphoric acids and the salts thereof used include:mono or di-esters containing alkyl or alkenyl group having 8 to 45carbon atoms in total, or alkali metal salts or amine salts thereof.Examples of N-mono long chain aliphatic acyl-basic amino acids include:basic amino acids whose amino group at α- or ω-position is bound withacyl group having 8 to 22 carbon atoms, such as 2-ethyl hexanoyl,capryloyl, lauroyl, myristoyl, palmitoyl, stearoyl, isostearoyl, oleoyl,behenoyl, cocoyl, beef tallow fatty acid acyl or hydrogenated beeftallow fatty acid acyl. Examples of fluorine compounds containingperfluoroalkyl group include: those described in U.S. Pat. No.3,632,744, JP-A-62-250074, JP-A-55-167209 and JP-A-2-218603.

In the hydrophobic treatment, the amount of hydrophobic treatment agentused is preferably 0.0005 to 0.2 parts by weight, and more preferably0.02 to 0.1 parts by weight based on 1 part of pearl pigment, from theviewpoint of imparting sufficient hydrophobicity and a good feel formake-up cosmetics.

For the pearl pigments described above, more than one type can be usedin combination. The amount of the pearl pigments contained in make-upcosmetics is preferably 0.1 to 30% by weight and more preferably 0.5 to30% by weight, from the viewpoint of allowing the make-up cosmetics tofully produce the blend effect and of avoiding an unnatural look due totoo much luster. The pearl pigment of the present invention can also beused in combination with conventionally used pearl pigments.

The make-up cosmetics of the present invention can be produced by aconventional process. They can be, for example, powdery face powder,cake-type face powder, face powder, powdery foundation, oil-basedfoundation, cream foundation, liquid foundation, concealer, lid rouge,lip cream, cheek rouge, eye shadow, eye liner or eyebrow pencil.

Preferably, the amount of the pearl pigment of the present inventioncontained in the make-up cosmetics, of the present invention is: 0.1 to30% by weight and more preferably 0.5 to by weight, when the cosmeticsare powdery face powder, cake-type face powder and face powder; 0.1 to30% by weight and more preferably 0.5 to 30% by weight, when thecosmetics are powdery foundation and oil-based foundation; 0.1 to 30% byweight and more preferably 0.5 to 25% by weight, when the cosmetics arecream foundation, liquid foundation and concealer; 0.1 to 20% by weightand more preferably 0.5 to 1.5% by weight, when the cosmetics are liprouge and lip cream; 0.1 to 30% by weight and more preferably 0.5 to 25%by weight, when the cosmetics are cheek rouge and eye shadow; and 0.1 to30% by weight and more preferably 0.5 to 20% by weight, when thecosmetics are eye liner and eyebrow pencil.

The make-up cosmetics of the present invention may further include alubricant whose viscosity is 1000 mPa·s or less at 25° C. From theviewpoint of feeling in use, the viscosity of the lubricant used ispreferably in the range of 0.1 to 1000 mPa·s and more preferably in therange of 2 to 500 mPa·s.

Any lubricant, can be used as long as its viscosity is 1000 mPa·s orless. Examples of such lubricants include liquid paraffin, squalane,olive oil, ester oil, diglyceride, triglyceride, silicone oil, andfluorine lubricant having a perfluoroalkyl group. Of these lubricants,liquid paraffin, squalane, ester oil, silicone oil and fluorinelubricant having a perflueroalkyl group are preferably used.

More than one type of lubricant, can be used in combination. The amountof the lubricants used is preferably 0.5 to 60% by weight and morepreferably 2 to 50% by weight per 100% of make-up cosmetics, from theviewpoint of being free from a sticky feeling when used.

To allow make-up cosmetics to have preferable spreadability and showexpected optical characteristics when they are applied to the skin, theblending ration of the pearl pigment to lubricants is preferably 1/10 to100/1.

The make-up cosmetics of the present invention may include, ifnecessary, ingredients blended in commonly used cosmetics, such assurfactant, water-soluble polymer, other powders, moisturizer,preservative, chemical, UV absorber, pigment, inorganic or organic salt,perfume, chelating agent, pH adjuster or water, besides the abovedescribed ingredients.

The following examples further describe and demonstrate embodiments ofthe present invention. The examples are given only solely for thepurpose of illustration and are not to be construed as limitations ofthe present invention.

EXAMPLES Example 1

80 g of flaky mica of 5 to 60 μm in particle size were added to andfully dispersed in 1.2 L of water, and the mica dispersion was heated to80° C., an hydrochloric acid was added so that the pH of the dispersionwas adjusted to 3. Then, 337 g of pre-prepared, ferric nitrate aqueoussolution (17 parts by mass of ferric nitrate: 26 parts by mass of water)were added slowly, at a rate of 9×10⁻⁴ mol iron ion concentration/min,to the mica dispersion while keeping the pH of the dispersion at 3 usingsodium hydroxide aqueous solution. After completing the addition, the pHof the mixed solution was adjusted to 5 using sodium hydroxide aqueoussolution. The pH-adjusted solution was filtered, and the obtained solidwas rinsed to remove the salt, suction filtered, dried, and baked at700° C. for 1 hour.

The resultant pearl pigment was such that a coating layer of very fineiron oxide particles 20 nm in geometric thickness was formed uniformlyon the surface of the flaky mica. The surface roughness of the coatinglayer was measured to be 3.44 nm.

Then, 80 g of the above iron-oxide coated pearl pigment were added toand fully dispersed in 1.2 L of water, and the pigment dispersion washeated to 75° C., and hydrochloric acid was added so that the pH of thedispersion was adjusted to 1.6. Then, 240 g of 40% by weight titaniumtetrachloride aqueous solution were added at a rate of 1.4 g/min to thedispersion while keeping the pH of the dispersion at 1.6 using 20% byweight sodium hydroxide aqueous solution. After that, the pH of thedispersion was adjusted to 7 using 20% by weight sodium hydroxideaqueous solution. Then, the dispersion was rinsed with water to removethe salt, suction filtered, dried, and baked at 700° C. for 90 minutes.Thus, a titanium oxide/iron oxide coated coloring pearl pigment having agold interference color of a high chrome was obtained.

Example 2

An iron-oxide coated pearl pigment was produced in the same manner asExample 1, except that the amount of the ferric nitrate aqueous solution(17 parts by mass of ferric nitrate 26 parts by mass of water) added waschanged from 337 g to 430 g. The obtained pigment was such that acoating layer of very fine iron oxide particles 30 nm in geometricthickness was formed uniformly on the surface of the flaky mica. Thesurface roughness of the coating layer was measured to be 4.30 nm.

Then, the same procedures as Example 1 were carried out, except that theamount of 40% by weight titanium tetrachloride aqueous solution addedwas changed from 240 g to 200 g, to obtain a titanium oxide/ironoxide-coated coloring pearl pigment having a gold interference color ofa high chroma.

Example 3

An iron-oxide coated pearl pigment was produced in the same manner asExample 1, except that the amount of ferric nitrate aqueous solution (17parts by mass of ferric nitrate 26 parts by mass of water) added waschanged from 337 g to 544 g. The obtained pigment was such that acoating layer of very fine iron oxide particles 50 nm in geometricthickness was formed uniformly on the surface of the flaky mica. Thesurface roughness of the coating layer measured 3.03 nm.

Then, the same procedures as Example 1 were carried out provided thatthe amount of 40% by weight titanium tetrachloride aqueous solutionadded was changed from 240 g to 63 g, to obtain a titanium oxide/ironoxide-coated pearl pigment having a red interference color of a highchroma.

Example 4

An iron-oxide coated pearl pigment was produced in the same manner asExample 1, except that the amount of ferric nitrate aqueous solution (17parts by mass of ferric nitrate 26 parts by mass of water) added waschanged from 337 g to 544 g. The obtained pigment was such that acoating layer of very fine iron oxide particles 50 nm in geometricthickness was formed uniformly on the surface of the flaky mica. Thesurface roughness of the coating layer measured 3.03 nm.

Then, the same procedures as Example 1 were carried out, except that theamount of 40% by weight titanium tetrachloride aqueous solution addedwas changed from 240 g to 320 g, to obtain a titanium oxide/ironoxide-coated pearl pigment having a red interference color a highchroma.

Example 5

An iron oxide-coated pearl pigment was produced in the same manner asExample 1, except that the amount of ferric nitrate aqueous solution (17parts by mass of ferric nitrate 26 parts by mass of water) added waschanged from 337 g to 430 g. The obtained pigment was such that acoating layer of very fine iron oxide particles 30 nm in geometricthickness was formed uniformly on the surface of the flaky mica. Thesurface roughness of the coating layer was measured to be 4.30 nm.

Then, the same procedures as Example 1 were carried out, except that theamount of 40% by weight titanium tetrachloride aqueous solution addedwas changed from 240 g to 350 g, to obtain a titanium oxide/ironoxide-coated pearl pigment having a green interference color of a highchroma.

Example 6

80 g of flaky mica of 5 to 60 μm in particle size were added to andfully dispersed in 1.2 L of water, and toe mica dispersion was heated to80° C., and hydrochloric acid was added so that the pH of the dispersionwas adjusted to 3. Then, 337 g of pre-prepared ferric nitrate aqueoussolution (17 parts by mass of ferric nitrate: 26 parts by mass of water)were added slowly, at a rate of 9×10⁻⁴ mol iron ion concentration/min,to the mica dispersion while keeping the pH of the dispersion at 3 usingsodium hydroxide aqueous solution. After completing the addition, the pHof the mixed solution was adjusted to 5 using sodium hydroxide aqueoussolution. The obtained slurry-like reaction product was filtered andrinsed to remove the salt. Then, the moisture content of the slurry-likereaction product was measured and the slurry-like reaction product wasweighed so that its solid content was 80 g. Subsequently, water wasadded to give a 1.2 L of reaction product solution, and the reactionproduct was fully dispersed in the water, and the dispersion was heatedto 75° C. After completing the heating, hydrochloric acid was added sothat the pH of the dispersion was 1.6. Then, the same procedure asExample 1 was carried out, and titanium tetrachloride aqueous solutionwas added to the dispersion and baked at 700° C. for 90 minutes. Thus, atitanium oxide/iron oxide-coated coloring pearl pigment having a goldinterference color of a high chroma was obtained.

Example 7

An iron oxide-coated pearl pigment was produced in the same manner asExample 1, except that the amount of ferric nitrate aqueous solution (17parts by mass of ferric nitrate 26 parts by mass of water) added waschanged from 337 g to 140 g. The obtained pigment was such that acoating layer of very fine iron oxide particles of 10 nm in geometricthickness (30 nm in optical thickness) was formed uniformly on thesurface of the flaky mica. The surface roughness of the coating layerwas measured to be 8.3 nm.

Then, the same procedures as Example 1 were carried out, except that theamount of 40% by weight titanium tetrachloride aqueous solution addedwas changed from 240 g to 260 g, to obtain a titanium oxide/ironoxide-coated pearl pigment having a gold interference color of a highchroma.

Example 8

An iron-oxide coated pearl pigment was produced in the same manner asExample 1, provided that the amount of ferric nitrate aqueous solution(17 parts by mass of ferric nitrate 26 parts by mass of water) added waschanged from 337 g to 140 g. The obtained pigment was such that acoating layer of very fine iron oxide particles of 10 nm in geometricthickness was formed uniformly on the surface of the flaky mica. Thesurface roughness of the coating layer measured 8.5 nm.

Then, the same procedures as Example 1 were carried out, except that theamount of 40% by weight titanium tetrachloride aqueous solution addedwas changed from 240 g to 150 g, to obtain a titian oxide/ironoxide-coated pearl pigment having a red interference color of a highchroma.

Example 9

An iron-oxide coated pearl pigment was produced in the same manner asExample 1, provided that the amount of ferric nitrate aqueous solution(17 parts by mass of ferric nitrate 26 parts by mass of water) added waschanged from 337 g to 65 g. The obtained pigment was such that a coatinglayer of very fine iron oxide particles of 5 nm in geometric thickness(15 nm in optical thickness) was formed uniformly on the surface of theflaky mica. The surface roughness of the coating layer was measured tobe 3.5 nm.

Then, the same procedures as Example 1 were carried out, except that theamount of 40% by weight titanium tetrachloride aqueous solution addedwas changed from 240 g to 305 g, to obtain a titanium oxide/ironoxide-coated pearl pigment having a gold interference color of a highchrome.

Example 10

An iron-oxide coated pearl pigment was produced in the same manner asExample 1, provided that the amount of ferric nitrate aqueous solution(17 parts by mass of ferric nitrate: 26 parts by mass of water) addedwas changed from 337 g to 65 g. The obtained pigment was such that acoating layer of very fine iron oxide particles 5 nm in geometricthickness (15 nm in optical thickness) was formed uniformly on thesurface of the flaky mica. The surface roughness of the coating layermeasured 3.5 nm.

Then, the same procedures as Example 1 were carried out, provided thatthe amount of 40% by weight titanium tetrachloride aqueous solutionadded was changed from 240 g to 170 g, to obtain a titanium oxide/ironoxide-coated pearl pigment having a red interference color of a highchrome.

Example 11

An iron-oxide coated pearl pigment was produced in the same manner asExample 1, except that the amount of ferric nitrate aqueous solution (17parts by mass of ferric nitrate 26 parts by mass of water) added waschanged from 337 g to 65 g. The obtained pigment was such that a coatinglayer of very fine iron oxide particles 5 nm in geometric thickness wasformed uniformly on the surface of the flaky mica. The surface roughnessof the coating layer was measured to be 3.5 nm.

Then, the same procedures as Example 1 were carried out, except that theamount of 40% by weight titanium tetrachloride aqueous solution addedwas changed from 240 g to 251 g, to obtain a titanium oxide/ironoxide-coated pearl pigment having a green interference color of a highchrome.

Comparative Example 1

120 g of flaky mica of 5 to 60 μm in particle size were added to 820 gof water and heated to 95° C. A solution of 350 g of urea, 170 g offerrous sulfate, 10 g of ferric nitrate and 7 g of 30% nitric acidaqueous solution in 308 g of water was added dropwise to the above micadispersion at a rate of about 25 g/min over 35 minutes. Then the mixedsolution was stirred for 2 hours, and 205 g of 30% potassium carbonateaqueous solution were added dropwise to the mixed solution over about 40minutes. Then, the solution was rinsed with water to remove the salt,suction filtered, dried, and baked at 700° C. for 1 hour. The obtainedpigment was such that a coating layer of about 0.1-μm iron oxideparticles 30 nm in geometric thickness was formed a little roughly onthe surface of the flaky mica. The surface roughness of the coatinglayer was measured to be 13.41 nm.

Then, the same procedures as Example 1 were carried out, provided thatthe amount of 10% by weight titanium tetrachloride aqueous solutionadded was changed from 240 g to 200 g, to obtain a titanium oxide/ironoxide-coated pearl pigment having a gold interference color.

Test Examples

The values a* and b* of light reflected from powder and the geometricthickness of coating layer were determined for the pearl pigmentsobtained in Examples 1 to 5 and Comparative Example 1 and commerciallyavailable, titanium-oxide coated mica (Flamenco Gold, Flamenco Redmanufactured by ENGELHARD) (1) The values a* and b* of light reflectedfrom powder were measured in accordance with “the method for measuringthe values a* and b* of the present invention”. As a spectrophotometriccolorimeter, used was GCMS-4, manufactured by Murakami Color ResearchLaboratory Co Ltd., provided with sheet polarizer (Polaroid, Type HN32).As a light source, a halogen lamp (HLWS7) by NARVA Speziallampen GmbHwas used. Measurement samples were prepared by using pieces of blackartificial leather (Okamoto, Type: OR-7) and coating the area 5 cm×10 cmof each piece uniformly with each pigment powder using a sponge so thatthe amount of the coating applied was on average 0.05 mg/cm².

The geometric thickness of each coating layer was measured with SEM. Thegeometric thickness was obtained by first measuring the thickness of theflaky powder before coating and then measuring the thickness of thepearl pigment after coating. The optical thickness was obtained bymultiplying the geometric thickness of the coating layer by therefractive index of the same. The refractive index of iron oxide (Fe₂O₃)used was 3.0 and that of titanium oxide was 2.5. The results are shownin Table 1.

(2) The values a* and b* of light reflected from powder were alsomeasured under the above described conditions in accordance with thecommonly used colorimetry (measurement angle of 45°) in which no sheetpolarizer was used. The values c* and h indicate the chroma and hueangle standardized by Commission International de L'Eclairage (CIE)(1976). The results are shown in Table 2.

The results shown in Table 2 prove that in the pearl pigments of thepresent invention, the values c* are larger than those of thecomparative example and commercially available pigments that have thesame hue angle, in other words, the pearl pigments of the presentinvention are brighter. This indicates that in the pearl pigments of thepresent invention, interference colors are obtained free from therestriction from the color of the color metallic compounds themselves.

TABLE 1 Geometric Geometric Thickness of Thickness of Iron OxideTitanium Coating Oxide Coating Appear- [Optical [Optical ance ofThickness] Thickness] Value Value Sample (nm) (nm) a* b* Example 1 Goldpearl 20 [60] 140 [350] 7.6 4.5 Example 2 Gold pearl 30 [90] 130 [325]6.3 1.3 Example 3 Red pearl  50 [150]  80 [200] 5.5 0.2 Example 4 Redpearl  50 [150] 140 [350] 5.0 4.1 Example 5 Green pearl 30 [90] 220[550] 8.8 7.4 Example 6 Gold pearl 20 [60] 140 [350] 3.8 2.4 Example 7Gold pearl 10 [30] 160 [400] 3.5 3.0 Example 8 Red pearl 10 [30] 130[320] 3.4 2.8 Example 9 Gold pearl  5 [15] 170 [425] 4.5 3.0 Example 10Red pearl  5 [15] 130 [325] 5.0 4.2 Example 11 Green pearl  5 [15] 160[400] 6.3 7.2 Compar- Gold pearl 30 [90] 130 [325] 10.8 9.3 ative Ex-ample 1 *Commercially available pigments are excluded because theycontain no colored metals in their inner layers.

TABLE 2 Geometric Geometric Thickness of Thickness of Iron OxideTitanium Oxide Appearance Coating [Optical Coating [Optical Value ValueValue Value of Sample Thickness] (nm) Thickness] (nm) a* b* c* h Example1 Gold pearl 20 [60] 140 [350] −6.5 47.3 48 98 Example 2 Gold pearl 30[90] 130 [325] −5.3 48.3 49 96 Example 3 Red pearl 50 [150]  80 [200]35.3 −4.1 36 353 Example 4 Red pearl 50 [150] 140 [350] 25.2 −11.5 28335 Example 5 Green pearl 30 [90] 220 [550] −7.9 4.7 9 149 Example 6Gold pearl 20 [60] 140 [350] −11.7 43.5 45.1 105 Example 7 Gold pearl 10[30] 160 [400] −6.8 49.6 50 98 Example 8 Red pearl 10 [30] 130 [320]33.5 −3.9 34 353 Example 9 Gold pearl 5 [15] 170 [425] −5.6 50.7 51 96Example 10 Red pearl 5 [15] 130 [325] 30.2 −13.8 33 335 Example 11 Greenpearl 5 [15] 160 [400] −15.8 9.4 18 148 Comparative Gold pearl 30 [90]130 [325] −5.9 25.7 26 103 Example 1 Commercially Gold pearl FlamencoGold −6.5 30.1 31 102 available pigment 1 Commercially Red pearlFlamenco Red 17.1 −0.6 17 358 available pigment 2Applications

Applications of coatings, inks and plastics in which pearl pigmentsobtained in examples are used will be shown below.

Application 1 (Coating for Automobiles)

A steel sheet with an intermediate coating applied to anelectrodeposition coating was prepared. A color base coating was appliedonto the surface of the intermediate coating, and the resultant steelsheet was baked at 140° C. for 30 minutes to be dried. Then, a basecoating was prepared which was a resin fluid made up of acrylic resinand melamine resin and containing 5% by weight of pearl pigment obtainedin Example 1 and spray coated on the surface of the above color basecoating so that the coating thickness was 15 μm. Subsequently, anacryl-melamine clear coating was applied to the surface of the basecoating by wet-on-wet spray coating so that the coating thickness was 40μm, and the resultant steel sheet was baked at 140° C. for 30 minutes sothat the base coating and the clear coating was integrally cured. Thecoated steel sheet thus obtained had a lustrous interference color ofbrilliant gold.

Application 2 (Printing Ink Composition)

The ingredients shown in Table 3 were mixed, and the mixture was kneadedwith a sand m±1.1 to obtain a printing ink composition.

Printing was performed on black paper using the obtained printing inkcomposition so that the thickness of the coating (after drying) was 50μm. The coating had a lustrous interference color of brilliant gold.

TABLE 3 Content Ingredients (parts by weight) Pearl pigment of 12.5Example 1 Acrylic resin 25.0 Naphtha 30.0 Butylcellosolve 32.5Application 3 (Plastic-Coloring Composition)

The ingredients shown in Table 4 were mixed with a Henschel mixer, andthe obtained mixture was formed into colored pellets with an extrudingmachine. Then the pellets were formed into platelet-shaped pieces90×50×2 mm in size in an extruder. The formed pieces had a lustrousinterference color of brilliant, red.

TABLE 4 Content Ingredients (parts by weight) Pearl pigment of 2.0Example 3 Polyethylene resin 97.5 Dibutylhydroxytoluene 0.5(antioxidant)

Examples 12 to 15, Comparative Examples 1 to 2

Cake-type foundations each having the compositions shown in Table 5 wereproduced. The produced cake-type foundations were evaluated in terms ofcreating: a smooth finish, a light skin color, the smallest possiblecolor difference between the forehead portion and the side cheekportion, and a natural luster. The evaluations are also shown in Table5,

(Production Process)

The ingredients (1) to (13) were mixed while stirring, and then theingredients (14) to (16) were added and mixed. Each mixture waspulverized with an atomizer and sieved, and the sieved powder was packedin a metal dish and compressed to obtain a cake-type foundation.

(Evaluation Method)

Twenty panels for cosmetics were allowed to use each of the producedcake-type foundations and scored points based on the criteria shownbelow. The quality of the foundations was judged using the average valueof the points scored by the panels.

(1) creates an attractive skin look, creates a smooth finish, creates alight skin color, creates natural luster;

5 points very good

4 points: good

3 points: fair

2 points: a little poor

1 point: poor

(2) color difference between the forehead portion and the side cheekportion

5 points: almost no difference

4 points small difference

3 points: somewhat difference

2 points: a little large difference

1 point: large difference

TABLE 5 Comparative Ingredients Examples Examples (% by weight) 12 13 1415 1 2 (1) Pearl pigment 10 (Example 1) (2) Pearl pigment 10 (Example 2)(3) Pearl pigment 10 (Example 9) (4) Pearl pigment 10 (Example 10) (5)Talc 20 20 20 20 20 20 (6) Sericite 31.5 31.5 31.5 31.5 41.5 31.5 (7)Spherical nylon 5 5 5 5 5 5 (8) Zinc stearate 3 3 3 3 3 3 (9) Micatitanium* 10 (10) Titanium dioxide 10 10 10 10 10 10 (11) Yellow ironoxide 7 7 7 7 7 7 (12) Red iron oxide 2 2 2 2 2 2 (13) Black iron oxide1 1 1 1 1 1 (14) Paraben 0.5 0.5 0.5 0.5 0.5 0.5 (15) Dimethyl 5 5 5 5 55 polysiloxane (10 mPa · s) (16) Liquid paraffin 5 5 5 5 5 5 (10 mPa ·s) Creates a smooth finish 4.7 4.7 4.7 4.3 1.3 4.5 Creates a light skincolor 4.5 4.3 4.8 4.3 1.9 4.7 Creates the smallest 4.6 4.7 4.5 4.7 4.82.2 color difference between the forehead portion and the side cheekportion Creates a natural luster 4.7 4.7 4.7 4.2 3.0 2.2 Creates anattractive 4.7 4.7 4.7 4.5 2.2 3.0 skin look *Flamenco Gold manufacturedby ENGELHARD

What is claimed is:
 1. A process for producing a pearl pigmentcomprising: (A) adding an aqueous solution of a colored metal oxideprecursor to an aqueous dispersion of a flaky powder so that the amountof metal ion is 5×10⁻⁴ to 12×10⁻⁴ mol/min per 100 g of the flaky powder;adding an alkaline solution to the mixed solution so that the pH of themixed solution is adjusted to 5 to 8; separating the solid from themixed solution; baking the separated solid at 500 to 1000° C. to obtaina pearl pigment; suspending the obtained pearl pigment in water; addingan aqueous solution of a colorless metal or colorless metal oxideprecursor to the suspension; adding an alkaline solution to the mixedsolution so that the pH of the mixed solution is adjusted to 5 to 8;separating the solid from the mixed solution; and baking the separatedsolid at 500 to 1000° C.; or (B) adding an aqueous solution of a coloredmetal oxide precursor to an aqueous dispersion of a flaky powder so thatthe amount of metal ion is 5×10⁻⁴ to 12×10⁻⁴ mol/min per 100 g of theflaky powder; adding an alkaline solution to the mixed solution so thatthe pH of the mixed solution is adjusted to 5 to 8; separating theobtained solid from the mixed solution; adding an aqueous solution of acolorless metal or colorless metal oxide precursor to a dispersion ofthe solid; separating the obtained solid from the mixed solution; andbaking the separated solid at 500 to 1000° C.
 2. The process of forproducing a pearl pigment according to claim 1 that comprises (A). 3.The process of for producing a pearl pigment according to claim 1 thatcomprises (B).
 4. The process for producing a pearl pigment according toclaim 1, wherein when the aqueous solution of the colored metal oxideprecursor is added to the aqueous dispersion of the flaky powder, thetemperature of the mixed solution is in the range of 50 to 100° C. 5.The process for producing a pearl pigment according to claim 1, whereinwhen the aqueous solution of the colored metal oxide precursor is addedto the aqueous dispersion of the flaky powder, the pH of the mixedsolution is in the range of 2 to
 4. 6. The process for producing a pearlpigment according to claim 1, wherein the colored metal oxide precursoris an iron oxide precursor.